Dispersible monoazo dyes



United States Patent 3,471,467 DISPERSIBLE MONOAZO DYES Hans E.Wegmuller and Werner Bossard, Riehen, Switzerland, assignors to J. R.Geigy A.G., Basel, Switzerland No Drawing. Original application Feb. 15,1963, Ser. No.

343,202, now Patent No. 3,320,232, dated May 16,

67. Divided and this application Jan. 9, 1967, Ser. N 0.

3,157 Claims priority, application Switzerland, Feb. 15, 1963, 1,904/63,1,905/63 Int. Cl. C09h 29/38, 62/08 US. Cl. 260-153 4 Claims ABSTRACT OFTHE DISCLOSURE Monoazo dyes containing1-triazinyl-3-methyl-5-iminopyrazole coupling components which dyes arefree from groups which dissociate in water and from sulfuric acid amide,carbonic acid amide and aryloxysulfonyl radicals and are reddish yellowto orange scarlet dyes of good fastness properties and are suitable forthe dyeing of hyrophobic organic synthetic textile fibers.

The present application is a division of copending application, Ser. No.343,202, filed Feb. 7, 1964, and noW Patent No. 3,320,232.

The invention concerns new dispersion dyestuffs which do not containmetal and are difficulty soluble in water, processes for theirproduction, processes for the dyeing of hydrophobic organic fibers usingthe new dyestuflfs and, as industrial product, the material dyed withthe aid of these dyestuits.

In the scale of shades hitherto available for the disperse dyeing ofpolyester fibers, there has been lacking a yellow to orange shade whichwould combine in dyeings on the said fibers, optimal wet fastnesses,fastness to light and to sublimation, with a satisfactor drawing poweron the said fibers, and good compatibility with blue shades due to anespecially good migratory power in these fibers.

Known yellow polyester dyes show sufficient drawing power and fastnessto sublimation, but were found wanting in one or several of the otherabove-named properties. Disperse azo dyes containing al-phenyl-3-methyl-5-pyrazolone coupling component, which would beparticularly desirable for economic reasons, fail even in the twolastnamed properties. Sulfonic acid aryl esterand sulfamylsubstitutedderivatives of the last-mentioned dyestufi class fail particularly incompatibility with blue shades. The resulting green shades are otfenuneven and skittery.

It is, therefore, a principal object of the present invention to providedisperse azo dyes of similar accessibility as the forementioned azo dyescontaining 1-phenyl-3-methyl- S-pyrazolone coupling components, which,however, combine most or all of the above listed desirable properties.

This object and others which will become apparent as the description ofthis invention proceeds, are attained by the azo dyestuffs according tothe present invention.

The terms alkyl, alkoxy and alkanoy as used in this specification and inthe appended claims to define substituentfs, means those having from 1to 4 carbon atoms, unless expressly stated otherwise.

These dyestuffs are reddish yellow to orange scarlet 6 metal-freedyestulfs free from groups dissociating acid 1n water and from sulfonicacid amide, carbonic acid amide 3,471,457 Patented Oct. 7, 1969 andaryloxy-sulfonyl radicals, which are dyestufls of the formula (IIIA)wherein A represents an azo dyestutf diazo component radical selectedfrom the class consisting of benzene diazo components, thiazole diazocomponents, or benzothiazole diazo component radicals.

R represents NH N-alkyl-amino wherein alkyl is of 1 to 6 carbon atoms,

N-hydroXyalkyl-amino wherein alkyl is of from 2 to 6 carbon atoms.

N-lower alkoxy-alklamino wherein alkyl is of from 2 to 4 carbon atoms,,B-cyano-ethyl amino, N,N-di-alkylamino.

N,N-bis-(hydroxy-alkyl)-amino wherein each alkyl is of from 2 to 3carbon atoms.

N-alkyl-N-hydroxy-alkyl amino wherein alkyl is of from 2 to 3 carbonatoms.

N-alkyl-N-alkoXy-alkyl-amino wherein the last mentioned alkyl is of from2 to 3 carbon atoms.

Piperidinyl-(l), morpholinyl-(l), alkoxy of from 1 to 6 carbon atoms,chloroand bromo-alkoxy, alkoxy-alkoxy,, cyano-alkoxy the last fourmembers having 2 to 4 carbon atoms in the alkoxy moiety linked to thetriazinyl nucleus, or finally alkylthio of from 1 to 6 carbon atoms, and

R represents a radical as defined above under R or hydroxy, mercapto,phenylamino, chlorophenylamino, bromophenylamino, lower alkylphenylamino, lower alkoxy-phenylamino, cyclohexylamino, benzylamino,chlorobenzylamino, lower alkyl-benzylamino, or N-lower alkyl-N-phenylamino, which dyestuifs are yellowish to reddish orange. They aredistinguished from correspondingly substitutedl-phenyl-3-methyl-5-amino-pyrazole dyestuffs by superior fastness tosublimation.

Particularly valuable dyestuffs according to the invention are obtainedwith diazonium compounds of the benzene series which contain at leastone electrophilic substituent in 0- or p-position to the diazo group, inparticular with 0- or p-nitro-phenyl diazonium compounds having twonegative substituents, especially those of the last-mentioned compoundswhich also contain a further cyano, methylsulfonyl or ethyl-sulfonylgroup, or chlorine or bromine atoms.

Preferred dyestuffs are derived in particular from 1- amino 4ethylsulfonyl 2 nitrobenzene, l amino- 4 methylsulionyl 2 nitrobenzene,1 amino 2- chloro 4 nitrobenzene and 1 amino 2 cyano 4- nitrobenzene,which are first diazotized and then coupled with a coupling componentfalling under Formula IIIA.

Because of their easy accessibility and good affinity to polyesterfibers, particularly valuable compounds falling under Formula IIIA arethose in which R and R are identical and represent alkylamino,hydroxyalkylamino, alkoxyalkylamino, dialkylamino, N alkyl Nhydroxyalkylamino or alkoxy groups.

hydroxy 7 \N/ 8 (1110) wherein Y represents one of the radicals of theformula I l Oz I l N and and each of R and R represents independently ofthe other, N-alkylamino of from 1 to 6 carbon atoms, N- loweralkoxy-alkylamino wherein alkyl is of from 2 to 4 carbon atoms,hydroxy-alkylamino of from 1 to 6 carbon atoms, dialkylamino whereineach alkyl is of from 1 to 6 carbon atoms, N-alkyl-N-hydroxy-alkylaminowherein hydroxy-alkyl is of from 2 to 3 carbon atoms, or an alkoXyradical.

The dyestuffs according to the invention are brought into finelydistributed form by milling with dispersing agents. Suitable dispersingagents are, e.g., anionic dispersing agents such as alkylarylsulfonates, condensation products of formaldehyde and naphthalenesulfonic acids, lignin sulfonates, or non-ionogenic dispersing agentssuch as fatty alcohol polyglycol ethers.

Dyestuffs according to the invention are suitable for the dyeing ofhydrophobic organic synthetic textile fibers from aqueous dispersion,e.g., for the dyeing of cellulose diand tri-acetate, particularlyhowever, for the dyeing of high molecular esters of aromaticpolycarboxylic acids with polyfunctional alcohols, e.g., of polyethyleneglycol terephthalates such as Terylene, Tergal, Trevira, Diolen, as Wellas of other polymers such as Kodel.

The dyestuffs can also be used, however, for the dyeing of syntheticpolyamide fibers such as nylon or Perlon.

Polyester fibers are dyed with aqueous dispersions of the dyestuffsaccording to the invention preferably at temperatures of over 100 C.under pressure. The dyeing can also be performed, however, at theboiling point of the water in the presence of carriers such asphenylphenol, polychlorobenzene compounds or other similar auxiliaries,or by the foulard process (pad-dyeing) followed by thermofixing at180-210 C.

Dyestuffs according to this invention are distinguished by their goodaffinity to hydrophobic polyester fibers, in particular to polyglycolterephthalates and, depending on their composition, they produce onthese fibers reddish yellow, orange to orange-scarlet dyeings of goodcolor strength which have very good fastness to washing, milling,sublimation, light, rubbing, perspiration, solvents, cross-dyeing,decatising and gas fading. In addition, vegetable fibers, in particularcotton, are very well reserved by the dyestuffs according to theinvention. Also level dyeings are obtained with the usual marketcarriers.

The dyestuffs of Formula IIIA as well as other structurally similardyestuffs which fall under the general formula (III) wherein Arepresents the aromatic radical of the carbocyclic or heterocyclicdiazonium compound, and R and R each represents an inert monovalentsubstituent, are obtained by coupling an aromatic diazonium compound ofthe carbocyclic or heterocyclic series with a compound of the formulawherein R and R have the aforesaid meaning, and the components are sochosen that the dyestuff does not contain any water-solubilizing groupswhich dissociate acid in water. As carbocyclic diazonium compounds,preferably those of the benzene series or also those of the naphthaleneseries are used. Heterocyclic diazonium compounds have mainly 5 or also6 membered rings, particularly rings containing nitrogen, which may befused with carbocyclic rings. Preferred heterocycles contain onenitrogen atom in the ring in a position adjacent to the azo bond and areof, in particular, the thiazole, triazole, tetrazole, thiadiazole,oxadiazole, pyrazole, pyridine, benzthiazole or indazole series.

The ring A of the aromatic diazonium compounds of the carbocylic seriesusable according to the invention can be unsubstituted or they can bemonoor poly-substituted by identical or different substituents. Examplesof substituents are among others: hydrocarbon radicals such as normal orbranched chain alkyl groups, preferably those having up to 4 carbonatoms, cycloalkyl groups, particularly those having 6 to 8 carbon atoms,unsubstituted phenyl or unsubstituted phenylalkyl groups and thosesubstituted by alkyl or halogen; also ether groups, mainly low alkoxyand low hydroxyalkoxy groups, then unsubstituted phenoxy and phenylthiogroups and such groups substituted by halogen, alkyl or alkoxy;acylamino groups, preferably not further substituted or halogenatedalkanoylamino, alkoxycarbonylamino and alkylsulphonylamino groups, aswell as unsubstituted benzoyl'amino and phenylsulphonylamino groups orsuch groups substituted by alkyl or halogen, and finally, alsohalogenotriazinylamino or halogenopyrimidylamino groups.

However, A in the meaning of a carbocyclic ring preferably containselectrophilic substituents which can be present therein either alone ortogether with the substituents given above. By electrophilicsubstituents are meant here, among others: carbonyl groups such asalkylcarbonyl or phenylcarbonyl groups which may be halogenated; thencarboxylic acid ester groups such as alkoxycarbonyl, cycloakoxycarbonyl,phenylalkoxycarbonyl and phenyloxycarbonyl groups whereby these estergroups can be substituted by alkoxy and/or halogen and the rings ofthese ester groups can also be alkyl substituted; then phenyl,alkylphenyl or halogenophenylsulphonyl groups; and finally, asparticularly suitable electrophilic substituents are halogens up to theatomic number 35, the nitro, trifiuoromethyl, or the cyano group and lowalkylsulphonyl groups.

Examples of such substituents in carbocyclic rings A, particularly inbenzene rings are: the methyl, ethyl, isopropyl, tert.butyl andtert.amyl group; the cyclohexyl, phenyl, monomethyl-phenyl anddimethylphenyl, chlorophenyl, dichlorophenyl, bromophenyl, benzyl,methylbenzyl or chlorobenzyl group; the methoxy, ethoxy, 2-hydroxyethoxy, tertbutoxy, phenoxy, cresoxy, chlorophenoxy,bromophenoxy, phenylthio, methylphenylthio or chlorophenylthio group;the acetylamino, chloroacetylamino, bromacetylamino,p-chloropropionylamino, propionylamino, carbomethoxyamino,carbethoxyamino, carbobutoxyamino, methylsulphonyla-mino,chloromethylsulphonylamino and ethylsulphonylamino group; the pheny-1-,tolyl-, chlorophenyl-, dichlorophenylor bromophenylsulphonylamino group,the benzoyl-, chlorobenzoy-land methylbenzoylamino group; the4,6-dich1orotriazinyl amino or 2,4,5-trichloropyrimidylamino group,particularly however, the electrophilic substitutent-s such as thenitro, trifluoromethyl and cyano group, chlorine, bromine and/orfluorine; the acetyl, isopropionyl, tert.butyryl, chloroacetyl, benzoyl,methylbenzoyl, bromobenzoyl and chlorobenzoyl group; themethoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl,tert.butoxycarbonyl, phenoxycarbonyl, methylphenyloxycarbonyl,benzoyloxycarbouyl and chlorobenzyloxycarbonyl group; themethylsulphonyl, ethylsu-lphonyl, chloromethylsulphonyl, butylsulphonyl,phenylsulphonyl, tolysulphonyl, or chlorophenylsulphonyl rou g Tli ering A of the aromatic diazonium compounds of the heterocyclic seriesalso can be unsubstituted or mono or polysubstituted by identical ordifferent substituents. As substituents of heterocyclic rings A arementioned, among others: lower alkyl and hydroxyalkyl groups,unsubstituted phenyl radicals and those substituted by alkyl or halogen;also alkyland halogenoalkyl sulphonyl groups and the nitro group.

As examples of substituents in heterocyclic rings A are mentioned themethyl, ethyl, isopropyl and tert.butyl group, the phenyl, methylphenyl,chlorophenyl, and dichlorophenyl group, the methylsulfonyl,ethy-lsulfonyl and butylsulfonyl group and the nitro group.

As substituents of the c-ar-bocyclic rings which may be fused, thesubstituents of carbocyclic rings A already given can be used.

Diazonium compounds of the carbocyclic or heterocyclic series usable inthe process described above for making dyestuffs of Formula III arederived, e.g., from the following amines: l-amino-Z-nitrobenzene,l-amino- 2-nitro-4-methylbenzene, 1-amino-2-nitro-4methoxy-, -4-ethoxyor -4-phenoxy-benzene, 1-amino-2-m'tro-4-chlorobenzene,1-amino-2-nitrobenzene-4 methylsulfone and 1- amino-Z-nitrobenzene 4ethylsulfone, l-amino-Z-nitro- 4-trifluoromethylbenzene, l-amino 4nitrobenzene, 1- amino-4-nitro-2-methylbenzene, 1 amino 4 nitro-2-methoxyor Z-ethoxybenzene, 1-amino-4-nitro-2-chloroor -2-bromo-benzene,1 amino-4-nitro-2-cyanobenzene, 1-amino-4-nitro 2,5 dichlorobenzene,1-amino-4-nitro- 2,6-dichloroor -2,6-dibromobenzene, 1-amino-4-m'tro-3-carbethoxyor -3-carbobutoxybenzene,1-a-mino-2,4-dinitro-6-chlorobenzene, l-amino 2,4 dinitro-6-fluorobenzene, 1-amino-3-nitro-4-fiuorobenzene, 1-a-mino-2,4-, -2,5- or-3,4-dicyanobenzene, also 2-amino-5-nitrothiazole, 3 amino 1,2,4triazole, 2 amino 5 methyl- 1,3,4 thiadoazole, 3-amino-benzpyrazole, 2aminobenzthiazole, 2-amino 6 methoxy-benzthiazole or 2-amino-6-methylsulfonyl benzthiazole or 1-amino-2,4-dinitro-benzene.

The triazinyl ring of the coupling component according to the inventioncan contain identical or difierent inert monovalent substituents.Substituents which are inert all under the dyeing conditions are meantby inert substituents. As substituents can be named, among others: alkylradicals, preferably those having up to 4 carbon atoms, cycloalkylradicals in particular those having 6 to 8 carbon atoms, unsubstitutedphenyl radicals or phenyl radicals substituted by alkyl or halogen; thehydroxyl group; the mercapto group; alkoxy, alkylthio, hydroxyalkoxy,cyanoalkoxy groups; the amino group, monoand disubstituted amino groups,the alkyl or phenyl substituents of which are either not furthersubstituted or are further substituted by cyano, hydroxyl, alkoxy and/orhalogen; cycloalkylamino groups, unsubstituted and alkylorhalogen-substituted benzylamino groups, heterocyclic nitrogen bases and,finally, acylamino groups, preferably alkanoylamino and ureido groups.

Example of substituents of the triazinyl ring are: the methyl, ethyl,isopropyl, and tert., butyl group, the cyclohexyl, phenyl, methylphenyl,chlorophenyl, bromophenyl group, the hydroxyl and mercapto group, themethoxy, ethoxy, nand isopropoxy, nand iso-butoxy, benzyloxy,chlorobenzyloxy, cyclohexyloxy group, the methylthio, ethylthio,propylthio group, di (carbethoxy) methyl group, the amino, methylamino,ethylamino, nand isopropylamino,

butylamino, hydroxyethyl-amino, hydroxypropylamino, methoxypropylamino,N,N-dimethylamino, N,N-diethylamino, N,N-dibutylamino,N,N-dihydroxyethylamino, N,N-dihydroxypropylamino,N,N-dicyanoethylamino, N-methyl-N-hydroxyethylamino, phenylamino,chlorophenylamino, methylphenylamino, methoxyphenylamino,ethoxyphenylamino, N-phenyl-N-methylamino, N-phenyl-N-ethylamino,N-bromophenyl-N-ethylamino, N-phenyl-N-butylamino, cyclohexylamino,benzylamino,

methylbenzylamino and chlorobenzylamino group, the piperidyl ormorpholinyl group, the acetylamino and ureido group.

Coupling components of Formula IV usable according to the invention areobtained, e.g. by condensation of cyanoacetone or cyanoacetonimine,

with 1-s-triazinyl (2) hydrazines, preferably in dilute mineral acid orin acetic acid at a raised temperature.

1 s triazinyl (2) hydrazines are compounds which are easily obtained,e.g. by reacting 4-R '-substituted and 6-R -substituted2-chloro-1,3,5-triazines with hydrazine.

A diazonium compound is coupled with the coupling component by the usualmethods, preferably in mineral acid to weakly acid aqueous medium.Advantageously in an acid coupling medium, the mineral acid is graduallybuffered, e.g. with alkali metal salts of low fatty acids, if necessaryin the presence of solubility promoters, e.g. lower alkanols such asethanol, ethylene glycol monomethyl or monoethyl ether or of amides oflow fatty acids, in particular dimethyl formamide.

The following non-limitative examples serve to illustrate the invention.Where not otherwise stated, parts and percentages are given therein byweight. The temperatures are in degrees centigrade. The relationship ofparts by weight to parts by volume is as that of grams to cubiccentimeters.

3,471,467 7 8 EXAMPLE 1 solution of 26.2 parts of 1[4,6'-bis-ethylamino-triazinyl (2')] 3 methyl 5 aminopyrazole in 1100parts of water, 250 parts of 80% acetic acid and 50 parts of 36%hydrochloric acid. The free mineral acid is then 5 buffered by theaddition of sodium acetate. On completion of the coupling, the orangecoloured precipitate, the composition of which corresponds to theformula 23 parts of 1 amino 4 ethylsulphonyl 2 nitrobenzene aredissolved in 120 parts of 60% sulphuric acid and the solution isdiazotised for 6 hours at 2025 with nitrosyl sulphuric acid,corresponding to 6.9 parts of sodium nitrite. The diazonium saltsolution so obtained is added dropwise at -5 to a solution of 24.3 partsof 1 [4,6 bis methylamino triazinyl (2')] 3- methyl aminopyrazole in1,200 parts of water, 150 OzN N=NCH-COH= parts of 80% acetic acid and 30parts of 36% hydro- 10 chloric acid. After about 1 hour, the pH of thereaction mixture is raised to 4-4.5 by the addition of sodium acef tate.On completion of the coupling, the red-orange precipitate is filteredoff, washed neutral with dilute sodium carbonate solution and then freeof salt with water. I H The coupling product, the composition of whichcorre- C2H5NH C\ /C NHCZH sponds to the formula N is filtered off,washed with a lot of water and dried under I HNAll l reduced pressure. Apreparation produced by milling with a condensation product ofnaphthalene-Z-sulfonic N acid and formaldehyde dyes polyglycolterephthalate or A; cellulose triacetate fibers in pure yellowish orangeshades from aqueous dispersion if desired in the presence of a carriersuch as o-phenylphenol. The dyeings have very good fastness to rubbing,light and sublimation.

N The 1-[4',6'-bis-ethylamino-triazinyl (2')]-3-methylis dried in vacuoat 70-80 and then milled with a mix- QPY usfid 111 thlS ample ascoupling comture of a ugnin sulphonate and a naphthalene sulphonicponent is obtained in the following manner: 80 parts ofacid-formaldehypde condensation product. The dye prep-24'bis'ethylamino'6'hydrazino'tFiaZiQC are dissolved in aration obtainedin this way dyes polyglycol terephthalate 120 Parts of aqueous 80%'acetlacld and 200 Parts of fibres, if desired with the addition of carrierssuch as Water- Separately, 34 Parts of y -imine, o-phenylphenol, invivid orange shades. The dyeings have a- 2 f added I0 200 parts of verygood fastness to washing, perspiration, light and subaqueous16%-hYdf0Ch10r1 acld- T e tvf/O Solutions are li i 0 mixed with eachother and heated during 20 hours at The 1 [426' bis methylaminotriazinyl 2' 3 0 to 40. The formed precipitate is separated by filtra- 3h l 5 aminopyrazole used i this example as tron, washed with cold water,and dried 1n 10 torr vacustarting material is obtained by reacting 2,4bis methylum at 70 to (111T 111g 18 hours Parts f t a ovamino-6-hydrazino-triazine with acetoacetic acid nitrile. 4O menlioneddesiljed starting material of 99% P y are obtained at a yield rate of91%. EXAMPLE 2 The pure compound of M.P. 242-244 is obtained A finesuspension of 17.3 parts of l amino 2-chloroby recrystallisation of thecrude condensation product 4-nitrobenzene in 300 parts of water, 30parts of 36% hyfrom ethyl alcohol. drochloric acid and 5 parts of cetylpolyglycol ether is Dyestuifs having similar properties are obtained ifdiazotised at 0-5 by adding dropwise a solution of 6.9 equivalentamounts of the diazo and coupling comparts of sodium nitrite in parts ofwater. The clear ponents described in the following Table I are usedunder diazonium salt solution is added dropwise at 05 to a theconditions described in the above example.

TAB LE I Shade on polyester No. Dlazo component Coupling componentfibres 3 1-amino-2-nitrobenzenel-[4,6-bif-methylaminotriazinyl-(2')]-3-methyl-5-amin0- Reddish yellow.pyrazo e. 4 l-amino-z-nitroi-methylbenzene ..do Yellowish orange. 5..l-amino-znitro-4-trifluoromethylb enzene .do... Do. 6.1-amino-2-nitrobenzene4-sulphonic acid phenyl ester .-do... Orange. 7.l-amino-2-eyano-4-nitrob enzene... -.do. D0. 8.1-amino-2-methoxy-4-nitrobenzene o Do. l-amino-2-nitro-4-ehlorobenzene.1-[4,6-bis-ethylaminotriazinyl-(2)]-3-methy1-5-amino- Do.

pyrazo e. 10 1-amino-2,4-dieyanobenzene .-do Orange. 111-an1in0-2nitrobenzene+sulphonic acid-N-methyl-N- -..-do Do.

hydroxyethylamide. 12 1-amin0-4-nitrobenzene .-do Yellowish orange. 13..1-amino4-nitro-26-dichlorobenzene.... .do..- Orange. 14....l-amin0-2.4-dinitro-6-chlorobenzene..- --do. Reddish orange. 15....2-amino-6-methoxybenzthiazole .-do Orange. 16--.1-amin0-2-nitro-4-methoxybenzene 1-[4 ,6-bif-propylaminotriazinyl-(2)l-3-methyl-5-amino- Do.

pyrazo e. 17.. l-amino-2-nitro4-tritluoromethylbenzene. Yellowishorange. 18.- l-amino--nitro-ii-earbobutoxybenzene Orange. 19..l-amino-2-nitrobenzene-4-sulphonic acid diethylamide -.do. Do. 20l-amino-irnitrobenzene1-[4,6-bif-butylaminotriazinyl-(2)]-3-methyl-5-amin Reddish yellow.pyrazo e. 21 1-amino-2-cyano-4-nitrobenzene ..do Orange.l-amino-4-nitro-2,5-diehlorobenzene. Do. l-amln0-2-nitr0-4-ehlorobenzene..do D0. 1-aminoA-nitro-Z-methoxybenzene1-[4,6-bis-methoxypropylamino-triazinyl-(2)]-3-methyl-5- Orange.

aininopyrazole.

4-amino-2-metl1yl-5-methoxy-4-nitroazobenzene 2-amino-5-nitrothiazole 271-amin0-4-nitr0-3-carbethoxybenzene Reddish orange.

.- Scarlet.

TABLE I-Gontinued Shade on polyester No. Diazo component Couplingcomponent fibres 28.- 1-amino-4-nitro-2,6-dich1orobenmne dn Do.

. 1-amin0-2-chloro-4-nitrobenzene1-[4,6'-bif-diethylaminotriazinyl-(2)]-3-methyl-5-arnino pyrazo e.1-[4,6-biis-dibutylaminotriazinyl-(2)I-B-methyl-fi-amino- Do.

pyrazo e. 31-- 1-amino-2-nitrobenzeue-i-sulphonic acid diethylamide Do.32 n 1-[4-dimethylamin0-6-methoxypropylamino-triazinyl- (2) 1-3- Do.

methyl-fi-aminopyrazole. 33 Z-amino-6-methylsu.lphonyl-benzthiazole oDo. 24 (in 1-[4 ethylarnino-6'-dibutylamino-triazinyl-(2)]-3-methy Do.

aminopyrazole. 35 1-a1nino-2-nitrobenzene1-[4-pIll1enylamin0-6'-methylamino-triazinyl-(2)]-3-methyl-5- Reddishyellow.

am opyrazo e. 36 l-amino-Z-chloro-4-nitrobenzene1-[4-(2-methylphenyl)amino-6-diethylamino-triazinyl- Yellowish orange.

(2)1-3-methyl-5-aminopyrazole. 371-[4,6-bis-N-methyl-N-hydroxyethylamino-triazinyl-(2)]-3 Do.

' methyl--aminopyrazole. 38 l-amino-Z-cyano-et-nitrobenzene "do Orange.39 --do 1-[4,6-bis-hydr0xyethylaminotriaZinyl-(Z)j-3-methy1-5- Do.

aminopyrazole. 40 2-arnino-5-nitrothiazole dn Scarlet. 41 (in1-[4'-cyclohexylamino-6-ethylamino-triazinyl-(2)1-3-methylo.

5-aminopyraz0le. 42 l-amin0-2-nitro-4-methylsulfonylbenzene1-[4-benzylamif06-methylan1ino-tr1azinyl-(2')1-3-methyI-5- Orange.

aminopyrazo e. 43 1-amino-2-nitro-4-methylsuliony1benzene1-[4-propylamipo-(Y-diethylamino-triaziuyl-(2)]-3-methyl-5- Do.

aminopyrazo e. 44 1-amino-2,4-dinitrobenzene1-[4,6'-bif-ethylaminotriazinyl-(2')]-3-methyl-5-amino- Do.

pyrazo e. 45 do 1-[4,6-bis-diethylaminotriazinyl-(2)]-3-methyl-5-amino-Do.

pyrazo e. 46 do 1-[4,6-bis-butylaminotriazinyl-(2)]-3-methyl-5-amino Do.

pyrazole.

EXAMPLE 47 16.3 parts of l-amino 2-cyano 4-nitrobenzene are added to 200parts of a mixture of concentrated sulphuric acid and nitrosyl sulphuricacid, corresponding to 6.9 parts of sodium nitrite, at 0-5. To completethe diazotisation, the reaction mixture is stirred overnight at -15 Thediazoniurn salt solution so obtained is poured onto about 1,200 parts offinely crushed ice, clarified, and added dropwise to a solution of 26.4parts of 1-[4',6-bis-ethoxy-triazinyl (2')]-3-methyl-5-aminopyrazole in1,200 parts of water and 75 parts of 36% hydrochloric acid. The freemineral acid is then buffered by the addition of sodium acetate. Oncompletion of the coupling, the precipitated scarlet precipitate isfiltered oflP, washed in the usual way with dilute sodium carbonatesolution and then with water, and dried. The composition of thedyestufis obtained corresponds to the pound, recrystallised frommethanol, melts at 212-214. formula Dyestuifs having similar propertiesare obtained If OZN equivalent amounts of the diazo and coupling comllponents given in the following Table II are coupled under ON theconditions described in Example 47.

50 III N C H OC /O-O 0 H;

TABLE II Shade on Polyester No. Diazo component Coupling componentfibres 1-amino-2-ehloro-4-nitrobenzene1-[4,6-bis-meth0xytriazinyl-(2')]-3-methyl-5-aminopyrazole Yellowishorange. 1-amino-2-ethoxy-4-nitroben1Pne range. 1-amino-2,4-dinitrobemene do D0. 1-amin0-2, 4-dinitro-fi-chlorobenzene Do.1amino-2-nitro-4-chlorobenzene Do. 1-amino-2 nitro-4-phenoxybenzene Do.1-amino4-nitro-3-carbobutoxybenze Do.1-amino-4-nitro-2,6-dichlorobenzene. Orange.

1-amino-2-nitro4-trifiuoromethylbenzen1-amino-2-nitrobenzene-4-sulphonie acid-o Yellowish orange.

Orange.

Z-aminobenzthiazole..- Reddish yellow.

1-amino-3-nitro4-fluoro ..do Orange.

l-amino2-nitrobenzene-4-sulphon1 [4,6-bis-propoxytriazinyl-(2)]-3-methyminopyrazo Do.

hydroxyethylamide.

61 1-amino-2-nitrobenzene--methylsulphone1-[4',6-bis-butoxy-triazinyl(2)]-3-methy1-5-aminopyrazole-. Orange. 62l-amino-2-cyano-4-nitrohenvane (in 63 Lamina-2,4-dinitrobenzeue.. do Do.64 1-arnino-2,fi-dichloro-t-nitrobenzene Do. 65 2-amino-5-nitrothiazole..do Scarlet. 66 l-amino-2-nitrobenzene-4-sulphonic acid amide.l-[4,6'-bis-piperidinotriazinyl-(2)]-3-methyl-5-aminopyrazo1e Do. 671-a1njno-2,4-dinitro-6-ehlorobenzene do Do, 68 do1-[4,6-bis-morpholinotrlazinyl-(2)l-3-methyl-5-aminopyrazole Do.

TABLE II-Conti11ued Shade on Polyester No. Dlazo component Couplingcomponent fibres 69 1-amtno-2,4-dlnitrobenzene1-[4-ethoxy-6-diethylan1ino-triazinyl-(2')]-3-methyl-5-amino- Orange.

pyraz e. 70 2-amino-5-nitrothiazole1-[4-methoxy-6'-phenylamino-triazinyl-(2')]-3-methyl-5 Scarlet.

aminopyrazole. 71 Lamino-Z-chloroA-nitrobenzene 1-[ buttixy-fiethylamlno-trlazinyL(2)]-3-methy1-5- amino- Yellowlsh orange. pyrazo e.72 1-amino-2-nitro-4-ethoxybenzene .do D0. 731-amino-2-nitro-4-ethy1sulfonylbenzene1-[4,6-bif-ethylaminotriazinyl-(2)]-3-methy1-5-amino- Yellowish orange.pyrazo e. 74 1-amlno-2-nitrobenzene1-[4,6-bis(e-methoxypropyl-amino)-tr1aziny1-(2)]3-methyl-5- Reddishyellow.

aminopyrazole. 7 do1-[4,6-bis-(B-cyanoethylamino)-triazinyl-(2)]-3-methyl-5- Do.

amino-pyrazole. 76 1amino-2-mtro-4-methyl-benzene1-[4,6-bis-(N,N-dl-fl-hydroxyethyl-arnino)-trlazlny1-(2)]-3- Yellowishorange.

methyl-5-amino-pyrazole. 77 -.do 1-[4,6-bis-(N-methyl-N--methyloxypropyl-amtno)-triazluyl- Do.

(2)]-3-methyl-5-amino-pyrazole. 78 1-am1no-2-n1tro-4-chloro-benzene1-[4,6-bif-(B-chloroethoxy)triazinyl-(2)]-3-methy1-5-amlno- Yellowishorange. pyrazo e. 79 d 1-[4,6-biis-(s-cyanoethoxy)-trlazlnyl-(2)]-3-methyl-5-amino- Do.

pyrazo e. 80 1amino-2-chloro-4-nitrobenzene1-[4,6-bis-(B-methoxyethoxy)-triazinyl-(2)]-3-methyl-5-arnino- D0.

pyraz e. 1-{4,6-b?-methylthiotrlazinyl-(2)]-3-methyl-5-amino- Do.

pyrazo e. 82 1-amino-2-bromo-4-n1tro-benzene1-[4-N,N+1iethylamino-6-mercapto-trlazinyl-(2)]-3-methyl-5- Do.

amino-pyrazole. 83 1-amino-2-bromo-4-n1tro-beuzene1-[4-pro1iy1amino-6-hydr0Xy-triazinyl-(2)]-3-methy1-5-amlno- Do.

pyrazo e. 84 1-amino-2eyano-4-nitro-benzene1-[4-ethylamlno-6-(4"-chloropheny1amino)-trlazinyl-(2)-3- Orange.

methyl-5-aminopyrazole. 85 do1-[4-N,N-dimethylamino-fi'-(2"-methoxyphenylamino)- D0.

triazinyl-(2')]-3-methyl-5-aminopyrazolo. 861-amin0-2-nitro-4-methylsulfonylbenzene1[4-methylamin0o-(4-chlorobenzylamino)-triaz1nyl-(2)]-3- Yellowishorange.

methyl-S-amino-pyrazole. 87 do1-[4-ethoxy-6-(N-phenyl-N-methyl-amino)-triazinyl-(2)]-3- Do.

methyl-fi-amino-pyrazole. 88 1-amin0-2-chloro-4-nltro-benzene1-[4,6'-bis-aminotriazinyl-(2')]3-methyl-5-arnino-pyrazole Do.

EXAMPLE 89 14.5 parts of 'Z-amino-S-nitrothiazole are added in portionsat 0-5 to a mixture of 85 parts of glacial acetic acid, parts ofpropionic acid and nitrosyl sulphuric acid, corresponding to 6.9 partsof sodium nitrate. The reaction mixture is then diluted with 85 parts ofglacial acetic acid and 15 parts of propionic acid and stirred for 3hours at 0-5 For the coupling, 31.8 parts of1-[4',6'-bis-diethylaminotriazinyl (2')]-3-methyl-5-aminopyrazole aredissolved in 360 parts of glacial acetic acid and 60 parts of propionicacid and the clear diazonium salt solution is added dropwise at 5. Thefree sulphuric acid is buffered by the addition of anhydrous sodiumacetate. On completion of the coupling, the reaction mixture is dilutedwith water and the dyestuff which precipitates, the composition of whichcorresponds to the formula HN: N

i 02115 N N N- C-N EXAMPLE 90 2 parts of the dyestutf obtained accordingto Example 1, as finely dispersed powder, are dispersed in 4,000 partsof water. 12 parts of the sodium salt of o-phenylphenol are added tothis dispersion as carrier and also 12 parts of diammonium phosphate areadded. 100 parts of polyglycol terephthalate yarn are dyed for 1 /2hours at 98. The dyeing is rinsed and after-treated with dilute sodiumhydroxide solution and a dispersing agent.

An orange dyeing is obtained in this way which is fast to Washing, lightand sublimation.

If in the above example, 100 parts of polyglycol terephthalate yarn arereplaced by 100 parts of cellulose triacetate fabric, dyeing isperformed under the conditions given above and finally the dyeing isrinsed with water, then an orange dyeing is obtained which has very goodfastness to washing and sublimation.

EXAMPLE 91 In a pressure dyeing apparatus, 2 parts of the dyestutfobtained according to example 2 are finely dispersed in 2,000 parts ofwater containing 4 parts of oleyl polyglycol ether. The pH of the dyebath is adjusted to 6-6.5 with acetic acid.

100 parts of polyglycol terephthalate fabric are intrw duced at 50, thebath is heated within 30 minutes to and dyeing is performed for 50minutes at this temperature. The dyeing is then rinsed with water,soaped and dried. Under these conditions a yellowish orange dyeing isobtained which is fast to washing, perspiration, light and sublimation.

The dyestuffs described in the other examples produce dyeings of equalquality by this process.

EXAMPLE 92 Polyglycol terephthalate fabric (such as Dacron) isimpregnated in a foulard at 40 with a liquor of the followingcomposition:

20 parts of the dyestulf contained according to Example 3,

finely dispersed in 13 7.5 parts of sodium alginate, 20 parts oftriethanolamine, 20 parts of octylphenol-polyglycol ether and 900 partsof water.

The fabric is wrung out to about 100% content, dried at 100 and then thedyeing is fixed for 30 seconds at a temperature of 210. The dyed goodsare rinsed with water, soaped and dried. Under these conditions anorange dyeing is obtained which is fast to washing, rubbing, light andsublimation.

The dyestuifs described in the other examples produce dyeings of equalquality by this process.

We claim:

1. A reddish yellow to orange scarlet metal-free monoazo dyestuif freefrom groups dissociating acid in water and from sulfuric acid amide,carbonic acid amide and aryloxy-sulfonyl radicals, which dyestuif is ofthe formula wherein A is an azo dyestufi" diazo component radicalselected from the group consisting of a benzene diazo component, athiazole diazo component and a homothiazole diazo component,

R is a member selected from the group consisting of NH N-alkyl-amino,wherein alkyl is of 1 to 6 carbon atoms,

N-hydroxy-alkyl-amino wherein alkyl is of from 2 to 6 carbon atoms,

N-lower alkoxy-alkylamino wherein alkyl is of from 2 to 4 carbon atoms,B-cyano-ethyl amino,

N,N-di-alkyl-amino, N,N-bis-(hydroxy-alkyl) amino wherein each eachalkyl is of from 2 to 3 carbon atoms,

N-alkyl-N-hydroxy-alkyl-amino wherein hydroxy alkyl is of from 2 to 3carbon atoms,

N-alkyl-N-alkoxy-alkyl-amino wherein the last-mentioned alkyl is of from2 to 3 carbon atoms,

piperidinyl-( l morpholinyl-( 1 alkoxy of from 1 to 6 carbon atoms,

chloroand bromo-alkoxy, alkoXy-alkoxy and cyanoalkoxy the last fourmembers having from 2 to 4 carbon atoms in the alkoxy moiety linked tothe tri- CiH5NH-LN/ NHCgH5 3. A dyestuff of the formula 4. A dyestuff ofthe formula UNITED STATES PATENTS 3,320,232 5/1967 Wegmuller et al260l53 CHARLES B. PARKER, Primary Examiner D. M. PAPUGA, AssistantExaminer US. Cl. X.R.

